CN107949600A - Acrylic resin foaming body, its manufacture method and fiber-reinforced composite - Google Patents

Acrylic resin foaming body, its manufacture method and fiber-reinforced composite Download PDF

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Publication number
CN107949600A
CN107949600A CN201680051927.5A CN201680051927A CN107949600A CN 107949600 A CN107949600 A CN 107949600A CN 201680051927 A CN201680051927 A CN 201680051927A CN 107949600 A CN107949600 A CN 107949600A
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China
Prior art keywords
acrylic resin
foaming body
resin foaming
monomer component
acrylic
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CN201680051927.5A
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北出博章
樽本裕之
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Sekisui Kasei Co Ltd
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Sekisui Plastics Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/18—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material
    • B32B5/20—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material foamed in situ
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/065—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of foam
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/18—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B32B5/28—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer impregnated with or embedded in a plastic substance
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0014—Use of organic additives
    • C08J9/0023—Use of organic additives containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0014—Use of organic additives
    • C08J9/0033—Use of organic additives containing sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
    • C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0016—Plasticisers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/101—Esters; Ether-esters of monocarboxylic acids
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
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    • C08K5/42—Sulfonic acids; Derivatives thereof
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/062—Copolymers with monomers not covered by C08L33/06
    • C08L33/064—Copolymers with monomers not covered by C08L33/06 containing anhydride, COOH or COOM groups, with M being metal or onium-cation
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    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/24—Homopolymers or copolymers of amides or imides
    • C08L33/26—Homopolymers or copolymers of acrylamide or methacrylamide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2305/00—Condition, form or state of the layers or laminate
    • B32B2305/02—Cellular or porous
    • B32B2305/026—Porous
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2605/00—Vehicles
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    • C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
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Abstract

A kind of acrylic resin foaming body, the heat resisting temperature in its thermo-mechanical analysis are more than 170 DEG C, and the quantity of the bubble of major diameter 2mm above sizes is that every 10cm × 10cm areas are less than 2.0.

Description

Acrylic resin foaming body, its manufacture method and fiber-reinforced composite
Technical field
The present invention relates to acrylic resin foaming body, its manufacture method and fiber-reinforced composite.
The application based on the Patent 2015-177633 CLAIM OF PRIORITYs in Japanese publication on the 9th of September in 2015, and by its Content is quoted to herein.
Background technology
Acrylic resin foam molding is due to excellent strength and translucency, light weight, thermal insulation are excellent, It is used for daylighting heat-insulating material, medical X-ray platform core.And then surface mount fibre reinforced plastics (hereinafter also referred to as " FRP "), the wall material of the cold insulation room as goods vehicle, the component of the hull for forming small boat.
As the manufacture method of such acrylic resin foaming body, following method is employed：Acrylic compounds will be included Polymerizable monomer component, foaming agent and the polymerization initiator mixing of monomer, make polymerism solution.Then, it is the polymerism is molten Liquid stream enters template, is heated together with the template, makes aforementioned polymeric polymerizing monomer components.Thereafter the foaminess that will be obtained Polymer is further heated to high temperature, thus makes its foaming.
When making core uses the fiber-reinforced composite of FRP pieces using acrylic resin foaming body, surfacing, After the surface stacking FRP pieces of acrylic resin foaming body, the layered product is heated under elevated pressure, thus makes acrylic compounds Foamed resin is Nian Jie with FRP pieces.Therefore, even if will not cause under the high temperature conditions to the requirement of acrylic resin foaming body The flexibility (adaptability) of operation of thermal contraction.
In order to improve the flexibility (adaptability) of operation of acrylic resin foaming body, it is proposed that various schemes.
The acrylic compounds using the polymerizable monomer comprising more than 36 mass % of methacrylic acid are proposed in patent document 1 Foamed resin.
Proposed in patent document 2 using poly- comprising the acrylic monomer with maleic anhydride and Methacrylamide The acrylic resin foaming body of conjunction property monomer.
But this conventional acrylic resin foaming body is in translucency, in appearance there are problem, even if applied to doctor The purposes with uniform translucency of special requirement such as X-ray platform cores is treated, can not also be met.Additionally, there are the gas with than surrounding In the case of the significantly big bubble (hereinafter also referred to as " stomata ") (such as bubble of more than bubble major diameter 2mm) of bubble, have in X-ray The worry that stomata is shown in the form of shadow on photo, and can not meet mechanical strength.
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2014-9285 publications
Patent document 2：Japanese Unexamined Patent Publication 2013-227493 publications
The content of the invention
Problems to be solved by the invention
The present invention be in view of above-mentioned actual conditions and make, its object is to, there is provided flexibility (adaptability) of operation, translucency, outer Sight and the acrylic resin foaming body of mechanical strength.
The solution used to solve the problem
The inventors of the present invention have made intensive studies, it turns out that, by reducing the generation of stomata, above-mentioned ask can be solved Topic.
The present invention has following scheme.
[1] a kind of acrylic resin foaming body, wherein, the heat resisting temperature by following assay method A measure is 170 DEG C More than,
Quantity by the bubble of the major diameter 2mm above sizes of following assay method B measure is every 10cm × 10cm areas For less than 2.0.
<Assay method A>
Using the acrylic resin foaming body of 7mm (length) × 7mm (width) × 2mm (thickness) as test film.Use Thermo-mechanical analysis device, is using front endQuartzy manufacturing probe as pressure head.Under compression test pattern, in test film Thickness direction on abut the pressure head of load 100mN, heat up from 30 DEG C with 5 DEG C/min of programming rate to test film.Survey Determine the thickness of test film relative to the test film before experiment thickness contraction 10% when temperature.
<Assay method B>
Using the acrylic resin foaming body that one side is more than 10cm as test film.In orthogonal three of test film In the section in a direction, observed with scanning electron microscope, obtain the sum of the bubble of major diameter 2mm above sizes, and Obtain the average value of every 10cm × 10cm areas.
[2] the acrylic resin foaming body according to [1], it is to make containing the polymerism comprising acrylic monomer The acrylic compounds that monomer component, thermal decomposable foaming agent, the polymerism polymerisation in solution of polymerization initiator and plasticizer, foaming form Foamed resin,
Aforementioned polymeric monomer component includes (methyl) acrylic acid 30 relative to the gross mass of aforementioned polymeric monomer component ~70 mass %,
Foregoing plasticizer is at least one kind of chemical combination in the group being made of sulphonic acid ester, adipate ester and citrate Thing.
[3] the acrylic resin foaming body according to [1] or [2], its mean air bubble diameter is 0.05~0.30mm.
[4] the acrylic resin foaming body according to [2], wherein, aforementioned polymeric solution contains relative to foregoing 100 mass parts of polymerizable monomer component are the foregoing plasticizer of 0.1~20 mass parts.
[5] the acrylic resin foaming body according to [2], wherein, aforementioned polymeric monomer component includes maleic acid Acid anhydride and (methyl) acrylamide.
[6] a kind of fiber-reinforced composite, it includes the acrylic resin foaming body any one of [1]~[5] And fibre reinforced plastics.
[7] a kind of manufacture method of acrylic resin foaming body, it is characterised in that make containing comprising acrylic monomer Polymerizable monomer component, thermal decomposable foaming agent, polymerization initiator and plasticizer polymerism polymerisation in solution and producing foamed Property polymer, foregoing expandable polymer is foamed and acrylic resin foaming body is made,
Aforementioned polymeric monomer component includes (methyl) acrylic acid 30 relative to the gross mass of aforementioned polymeric monomer component ~70 mass %,
Foregoing plasticizer is at least one kind of chemical combination in the group being made of sulphonic acid ester, adipate ester and citrate Thing.
[8] manufacture method of the acrylic resin foaming body according to [7], wherein, aforementioned polymeric solution contains Relative to the foregoing plasticizer that 100 mass parts of aforementioned polymeric monomer component are 0.1~20 mass parts.
[9] manufacture method of the acrylic resin foaming body according to [7], wherein, aforementioned polymeric monomer component Include maleic anhydride and (methyl) acrylamide.
[10] a kind of sporting goods, it includes the acrylic resin foaming body any one of [1]~[5].
[11] a kind of vehicle component, it includes the acrylic resin foaming body any one of [1]~[5].
The effect of invention
In accordance with the invention it is possible to provide the acrylic compounds tree of flexibility (adaptability) of operation, translucency, appearance and mechanical strength Fat foaming body.
Brief description of the drawings
Fig. 1 is the sectional view for an example for showing the acrylic resin foaming body of the present invention.
Fig. 2 is the sectional view for an example for showing the fiber-reinforced composite of the present invention.
Fig. 3 is the figure of the relation of the apparent density and bending strength that show the acrylic resin foaming body in embodiment.
Embodiment
《Acrylic resin foaming body》
Hereinafter, the acrylic resin foaming body of the present invention is illustrated.
For the acrylic resin foaming body of the present invention, the heat resisting temperature in thermo-mechanical analysis is more than 170 DEG C, preferably For more than 180 DEG C, more preferably more than 190 DEG C.More specifically, the heat resisting temperature in thermo-mechanical analysis preferably 170~220 DEG C, more preferably 180~210 DEG C, it is 190~200 DEG C further preferred.
It should be noted that the heat resisting temperature in thermo-mechanical analysis measures as follows.
<The assay method of heat resisting temperature>
Using the acrylic resin foaming body of 7mm (length) × 7mm (width) × 2mm (thickness) as test film.Use Thermo-mechanical analysis device, is using front endQuartzy manufacturing probe as pressure head.Under compression test pattern, in test film Thickness direction on abut the pressure head of load 100mN, heat up from 30 DEG C with 5 DEG C/min of programming rate to test film.Survey Determine the thickness of test film relative to the test film before experiment thickness contraction 10% when temperature.
For the acrylic resin foaming body of the present invention, the major diameter 2mm above sizes measured by the following method The quantity of bubble be every 10cm × 10cm areas be less than 2.0, be preferably less than 1.8, be more preferably less than 1.6, into One step is preferably less than 1.4, particularly preferably less than 1.2.
<The assay method of the quantity of the bubble of major diameter 2mm above sizes>
Using the acrylic resin foaming body that one side is more than 10cm as test film.To any thickness direction of test film The first section, the second section of the thickness direction orthogonal with foregoing first section and the 3rd section of horizontal direction, with scanning Type electron microscope is observed, and obtains the sum of the bubble of major diameter 2mm above sizes, and obtains every 10cm × 10cm areas Average value.
It should be noted that the first section and the section that the second section is when the thickness direction of test film is cut off.At this time, First section is orthogonal with the second section.3rd section in the horizontal direction cut off test film when section, at this time, the first section with Second section is orthogonal.
Specifically, the acrylic resin foaming of 10cm × 10cm × 10cm is cut out from acrylic resin foaming body Body, as test film.With formed cut off in any direction the first section, second section orthogonal with foregoing first section and The mode in threeth section orthogonal with foregoing first section and foregoing second section cuts off the test film.To 3 sections, use Scanning electron microscope is observed, and obtains the sum of the bubble of major diameter 2mm above sizes, and obtains every 10cm × 10cm faces Long-pending average value.
The mean air bubble diameter of the acrylic resin foaming body of the present invention is preferably 0.05~0.30mm, is more preferably 0.1~0.25mm.When mean air bubble diameter is more than above-mentioned lower limit, become to be readily obtained the good of acrylic resin foaming body Good appearance.When mean air bubble diameter is below above-mentioned upper limit value, become easily to improve the machinery of acrylic resin foaming body Intensity.
It should be noted that mean air bubble diameter calculates as follows.
Acrylic resin foaming body is cut off, 18 times is amplified to scanning electron microscope, section is shot, By on the image printing of the section of shooting to paper.Then, 6 any line segments (length 60mm) are drawn to every paper, according to The quantity of the bubble overlapping with the line segment, the mean chord for calculating by following formula each line segment.Wherein, line segment as far as possible with bubble not Drawn only in a manner of contacts, in the case of contact, in the quantity of bubble.
The length of mean chord (t)=line segment/(multiplying power of quantity × photo of bubble)
Then, bubble diameter D is calculated by following formula.
D=t/0.616
Then, the arithmetic mean of instantaneous value for the bubble diameter D calculated by each line segment is obtained, using the arithmetic mean of instantaneous value as third The mean air bubble diameter of olefin(e) acid resin foam body.
In addition, the apparent density of the acrylic resin foaming body of the present invention is preferably 0.02~0.2g/cm3, more preferably For 0.05~0.15g/cm3.When apparent density is more than above-mentioned lower limit, mechanical strength becomes easily to improve.Apparent density is When below above-mentioned upper limit value, become to be readily obtained the good appearance of acrylic resin foaming body.
It should be noted that apparent density is measured using the method for the method recorded according to JIS K7222-1999.Tool For body, for the 10cm cut off in a manner of not changing original foam structure3Test film above measures its quality, passes through Following formula calculates apparent density.
Apparent density (g/cm3)=experiment tablet quality (g)/test film volume (cm3)
In addition, the acrylic resin foaming body of the present invention is preferably, by bending strength (unit：MPa) it is set to Y, incites somebody to action Apparent density (units/kg/m3) when being set to X, meet the relation of Y >=0.030X-0.351.
By meeting above-mentioned relation, so that mechanical strength becomes easily to further improve.
It should be noted that bending strength can be according to JIS A 9511：Described in 2006 " foamed plastic thermal insulation materials " Method measure.
The acrylic resin foaming body of the present invention is made containing the polymerizable monomer component comprising acrylic monomer, heat Polymerism polymerisation in solution, the foaming of decomposition-type foaming agent, polymerization initiator and plasticizer and manufacture.Particularly preferably by with It is described later《The manufacture method of acrylic resin foaming body》Manufacture method same method manufacture.
《The manufacture method of acrylic resin foaming body》
Hereinafter, the manufacture method of the acrylic resin foaming body of the present invention is illustrated.
In the manufacture method of the acrylic resin foaming body of the present invention, make containing the polymerism comprising acrylic monomer The polymerism polymerisation in solution of monomer component, thermal decomposable foaming agent, polymerization initiator and plasticizer, makes expandable polymer (polymerization process).
Then, the expandable polymer is foamed, make acrylic resin foaming body (hereinafter also referred to as " foaming Body ".) (foamed process).
<Polymerization process>
Polymerism solution is by by the polymerizable monomer component comprising acrylic monomer, thermal decomposable foaming agent, polymerization Initiator and plasticizer are mixed to obtain.
Hereinafter, the constituent of polymerism solution is illustrated.
[polymerizable monomer]
The polymerizable monomer component of the present invention includes acrylic monomer component.
(acrylic monomer)
As foregoing acrylic monomers, maleic anhydride, (methyl) acrylamide, (methyl) acrylic acid, horse can be included Come sour, fumaric acid, itaconic acid, itaconic anhydride, crotonic acid, (methyl) ethyl acrylate, (methyl) methyl acrylate, (methyl) third Olefin(e) acid butyl ester, (methyl) lauryl acrylate, (methyl) 2-EHA, (methyl) cyclohexyl acrylate, (methyl) Benzyl acrylate, maleic acid, Malaysia acid imide etc..Wherein, preferably (methyl) acrylic acid, (methyl) methyl acrylate, Maleic anhydride and (methyl) acrylamide.
It should be noted that the term of " (methyl) acrylic acid " in this specification refers to " methacrylic acid " and " propylene Any one in acid ".
Acrylic monomer can be used singly or in combination of two or more.
In polymerizable monomer component, the content of acrylic monomer is preferably relative to the gross mass of polymerizable monomer component 20~90 mass %.When the content of acrylic monomer is more than above-mentioned lower limit, become easily to improve acrylic resin hair The flexibility (adaptability) of operation of foam.When the content of acrylic monomer is below above-mentioned upper limit value, become easily to improve translucency.
In polymerizable monomer component, the content of (methyl) acrylic acid is preferably relative to the gross mass of polymerizable monomer component 30~70 mass %, more preferably 36~60 mass %.When the content of (methyl) acrylic acid is more than above-mentioned lower limit, become to hold Easily improve the flexibility (adaptability) of operation of acrylic resin foaming body.When the content of (methyl) acrylic acid is below above-mentioned upper limit value, become Obtain and easily improve translucency.
In polymerizable monomer component, the content of (methyl) methyl acrylate is excellent relative to the gross mass of polymerizable monomer component Elect 10~45 mass %, more preferably 20~40 mass % as.The content of (methyl) methyl acrylate is more than above-mentioned lower limit When, become easily to improve the flexibility (adaptability) of operation of acrylic resin foaming body.The content of (methyl) methyl acrylate is on above-mentioned When below limit value, become easily to improve translucency.
In polymerizable monomer component, the content of maleic anhydride relative to the gross mass of polymerizable monomer component be preferably 5~ 10 mass %.When the content of maleic anhydride is more than above-mentioned lower limit, become easily to improve adding for acrylic resin foaming body Work adaptability.When the content of maleic anhydride is below above-mentioned upper limit value, become easily to improve translucency.
In polymerizable monomer component, the content of (methyl) acrylamide is preferred relative to the gross mass of polymerizable monomer component For 1~5 mass %.When the content of (methyl) acrylamide is more than above-mentioned lower limit, become easily to improve acrylic resin The flexibility (adaptability) of operation of foaming body.When the content of (methyl) acrylamide is below above-mentioned upper limit value, become easily to improve translucency.
(styrene)
Styrene can also be contained in polymerizable monomer component.
In polymerizable monomer component, the content of styrene is preferably 10~20 relative to the gross mass of polymerizable monomer component Quality %.When the content of styrene is more than above-mentioned lower limit, the processing for becoming easily to improve acrylic resin foaming body is fitted Ying Xing.When the content of styrene is below above-mentioned upper limit value, become easily to improve translucency.
(polymerizable monomer in addition to acrylic monomer and styrene)
It should be noted that as the polymerizable monomer in addition to aforesaid propylene acrylic monomer and styrene, for propylene The purpose of modification of acid resin foaming body, can also contain in polymerism solution can be total to aforesaid propylene acrylic monomer on a small quantity Poly- monomer.
It should be noted that acrylic monomer, styrene and the polymerism in addition to acrylic monomer and styrene Total content of monomer is no more than 100 mass % relative to the gross mass of polymerizable monomer component.
[thermal decomposable foaming agent]
Thermal decomposable foaming agent produces the compound of gas for that can be decomposed more than 65 DEG C.Wherein preferably 100~180 DEG C decompose and produce the compound of gas.
As thermal decomposable foaming agent, urea, urea derivative, dinitrosopentamethylene tetramine, acid amides can be included Guanidine, trimethylene triamine, unifor, azodicarbonamide, thiocarbamide, ammonium chloride, dicyandiamide, dioxanes, hexane, hydration Chloral, citric acid etc..Wherein, preferred urea.
Thermal decomposable foaming agent can be used singly or in combination of two or more.
In polymerism solution, the content of thermal decomposable foaming agent is preferably relative to 100 mass parts of polymerizable monomer component 0.5~30 mass parts.
When the content of thermal decomposable foaming agent is in above-mentioned number range, become easily to improve translucency.
In the case that thermal decomposable foaming agent is urea, the content of thermal decomposable foaming agent is relative to polymerizable monomer component 100 mass parts are preferably 1~15 mass parts.
[polymerization initiator]
As polymerization initiator, redox system polymerization initiator, heat decomposition type initiator, photodegradation type can be used to draw Send out agent etc..Wherein preferred redox system polymerization initiator.
As redox system polymerization initiator, tert-butyl hydroperoxide, cumyl hydroperoxide, diisopropyl can be included Benzene hydrogen peroxide, p-menthane hydroperoxide, 1,1,3,3- tetramethyl butyl hydroperoxides etc..Wherein preferred tert-butyl hydroperoxide.
Polymerization initiator can be used singly or in combination of two or more.
In polymerism solution, the content of polymerization initiator is preferably 0.05 relative to 100 mass parts of polymerizable monomer component ~5 mass parts.
[plasticizer]
As plasticizer, adipate ester, trimellitate, polyester, phosphate, citrate, epoxidation can be included and planted Thing oil, sebacate, azelate, maleate, benzoic ether, sulphonic acid ester etc..Wherein, preferably sulphonic acid ester, adipate ester, lemon Lemon acid esters.
As sulphonic acid ester, alkyl sulfonic ester can be included.In alkyl sulfonic ester, the carbon number preferably 12~20 of alkyl.Ester portion The carbon number preferably 1~20 divided.Wherein optimizing alkyl phenyl sulfonate.As the commercially available product of sulphonic acid ester, LANXESS companies can be included Mesamoll etc..
In adipate ester, the carbon number preferably 1~20, more preferably 3~10 of ester moiety.Specifically, adipic acid can be included Methyl esters, adipic acid ethyl ester, adipic acid n-propyl, adipic acid isopropyl ester, adipic acid N-butyl, adipic acid isobutyl ester, adipic acid uncle Butyl ester etc..Wherein preferred adipic acid isobutyl ester.
In citrate, the carbon number preferably 1~20, more preferably 3~10 of ester moiety.In citrate, the preferred hydrogen of hydroxyl Atom is substituted with a substituent.As substituent, acetyl group etc. can be included.As acetyl citrate, specifically, can enumerate Go out acetyl tributyl citrate methyl esters, acetyl tributyl citrate ethyl ester, acetyl tributyl citrate n-propyl, acetyl tributyl citrate isopropyl ester, acetyl tributyl citrate N-butyl, acetyl tributyl citrate isobutyl ester, acetyl tributyl citrate tert-butyl ester etc..Wherein preferred acetyl tributyl citrate N-butyl.
(metal ion, chloride ion)
It is selected from addition, can also contain in present embodiment, in aforementioned polymeric solution by Cu+、Cu2+、Fe3+、Ag+、Pt2 +And Au3+More than a kind metal ion and chloride ion in the group of composition.
The oxidation-reduction potential of aforementioned metal ion be on the occasion of.
In addition, aforementioned metal ion played in polymerism solution as connect the nucleophobic material i.e. function of oxidant, Or as and material, that is, reducing agent of electronics function, peomote the polymerisation of aforementioned polymeric monomer.
On the other hand, foregoing chloride ion by with aforementioned metal ions binding, depart from, peomote aforementioned polymeric The polymerisation of property monomer.
Above-mentioned metal ion and chloride ion can be in the form of copper chloride, iron chloride, silver chlorate, chloraurides etc. with same Both one materials disposably contain in polymerism solution, can also be contained using different materials in polymerism solution.
In addition to chloride as described above, such as copper bromide, cupric iodide, copper stearate, aphthenic acids can also be passed through The materials such as copper, silver bromide contain metal ion as described above in polymerism solution.
It should be noted that for copper, silver, gold, in the form of salt as described above but also be able to can not only utilize golden Category is in itself or alloy makes its ion contain in polymerism solution.
For example, can be by making by copper, copper alloy (constantan：Copper/nickel alloy, brass：Cu zn alloy), silver, gold formed Particulate, line, net etc. are mixed into polymerism solution, make to contain these ions in polymerism solution.
It should be noted that as the specific material for making polymerism solution contain chloride ion, such as except Beyond sodium chloride, hydrochloric acid etc., 1,3- methylimidazoles chlorine, 1- butyl -3- methylimidazoles chlorine, 1- butyl -2,3- can be also included Methylimidazole chlorine, 1- ethyl-3-methylimidazoles chlorine, 1- methyl -3- n-octyl imidazoles chlorine, 1- methyl isophthalic acids-hydroxyethyl -2- oxen The surfactant of the imidazoles salt form such as fat alkyl-imidazole chlorine, hexadecyltrimethylammonium chloride, trimethyl chlorination Ammonium, stearyl trimethyl ammonium chloride, palm alkyl trimethyl ammonium chloride, tallow alkyl trimethyl ammonium chloride, docosyl three Ammonio methacrylate, diallyl dimethyl ammoniumchloride, dialkyl dimethyl ammonium chloride, cetyl trimethyl ammonium chloride, bay Surfactant of the quaternaries such as base trimethyl ammonium chloride etc..
It should be noted that as making the specific material containing chloride ion in polymerism solution, being preferably chlorine Change sodium, hydrochloric acid and hexadecyltrimethylammonium chloride, dialkyl dimethyl ammonium chloride, cetyl trimethyl ammonium chloride, lauryl Any one in trimethyl ammonium chloride, particularly preferably using cetyl trimethyl ammonium chloride.
In the case of making the material containing these chloride ions in polymerism solution, in general, can be with by polymerism Contain when the total amount of polymerizable monomer in solution is set to 100 mass parts as the ratios of 0.005~5 mass parts.
In addition, as making the specific material containing aforementioned metal ion, preferably silver chlorate, chlorination in polymerism solution Copper, copper stearate, copper naphthenate, iron chloride or copper (copper particle, copper wire).
Make in the case of containing them in polymerism solution, usually can be with by the polymerizable monomer in polymerism solution Total amount is set to become 1 × 10 during 100 mass parts-10~1 × 10-2The ratios of mass parts contains.
(dehydrating agent)
And then in the present embodiment, dehydrating agent can be also contained in aforementioned polymeric solution.
As the dehydrating agent, it is preferable to use the zeolites such as the sulfate such as anhydrous sodium sulfate, anhydrous magnesium sulfate, molecular sieve. For content of the dehydrating agent in polymerism solution, such as preferably the total amount of the polymerizable monomer in polymerism solution to be set To contain during 100 mass parts as the ratios of 0.01~50 mass parts.For such dehydrating agent, it is generally desirable to, it is polymerizeing It is mixed during the preparation of property solution, after being dehydrated to the moisture in solution, carries out filtering removal.
[other optional members]
Solvent, chain-transferring agent, reducing agent, dehydrating agent, polymerization inhibitor, bubble adjustment can be contained in polymerism solution Agent, other acrylic resin foaming bodies.
When heating is carried out to polymerism solution polymerize polymerizable monomer, the polymerization preferably carries out in a nitrogen atmosphere. Preferably 35~70 DEG C, more preferably 40~60 DEG C of polymerization temperature.
The polymerization can carry out under constant polymerization temperature, can also change polymerization temperature under 35~70 DEG C of scope Spend to carry out.
When polymerization time preferably 10~45 is small, more preferably 10~35 it is small when, it is further preferred 15~25 it is small when.Polymerization time During to be more than the preferable lower limit of aforementioned range, polymerisation easily fully carries out, and is not likely to produce stomata etc..Polymerization time is When below the preferred upper limit value of aforementioned range, productivity becomes higher.
When carrying out heating to polymerism solution in template makes its polymerization, template is according to the desired shape of expandable polymer Shape suitably selects.
Polymerism solution uses the filter element with mesh of the mesh size less than 0.300mm preferably before template is flowed into Filtered.Thus, the foreign matter in polymerism solution is removed, and can suppress the generation due to the stomata of the foreign matter etc..
As the filter element with mesh of the mesh size less than 0.300mm, such as 60 mesh filter (nets can be included Eye size 0.300mm), 200 mesh filters (mesh size 0.077mm) etc..
<Foamed process>
In foamed process, the expandable polymer for making to obtain in aforementioned polymeric process foams, and obtains acrylic resin Foaming body.
For the foamed process, between the hot plate of the mould of the hot plate a pair of of up and down with interval any distance, before making Expandable polymer foaming is stated, makes the hot plate of foaming body contact upside, with the hot plate extruding foaming body of upside.Then, can wrap Include the extruding force release operation of the power for the hot plate extruding foaming body for releasing upside.
In the manufacturing method of the present invention, when manufacturing flat acrylic resin foaming body, any with interval Flat expandable polymer is put between the hot plate of the mould of the hot plate a pair of of up and down of distance, this is foamed using foregoing hot plate Property polymer is heated to more than the heat decomposition temperature of thermal decomposable foaming agent.
When being heated using foregoing hot plate to expandable polymer, profit is there may be on the surface of expandable polymer Heated in the state of lubrication prescription.By being heated in the state of there are lubricant on the surface of expandable polymer, energy It is enough to prevent from producing cracking etc. on the surface of acrylic resin foaming body better.
The coating method of lubricant is not particularly limited, such as can be included using the manually operation such as bristle, cloth The method being coated.
As lubricant, such as dimethicone, Methylphenylsilanone etc. can be included.Lubricant can be used alone 1 Kind, two or more can also be applied in combination.For the coating weight of lubricant, consider the expansion ratio of expandable polymer or lubricate Species of agent etc. suitably determines.
The mould used in foamable is just not particularly limited as long as there is upper and lower a pair of of hot plate, according to target foaming body Shape carry out suitably select.By the heating that expandable polymer is carried out in the mould with desired inside dimensions Foaming, can obtain the foaming body of intended shape.
Make more than the temperature that heating-up temperature during expandable polymer foamable is expandable polymer softening and set It is more than the heat decomposition temperature for thermal decomposable foaming agent contained in expandable polymer.
For heating-up temperature, for example, in the case that thermal decomposable foaming agent is urea (135 DEG C of heat decomposition temperature), preferably More than 135 DEG C, more preferably more than 145 DEG C.Heating-up temperature is higher, and foaming is got over efficiency and carried out well.In addition, heating-up temperature is preferred Less than 220 DEG C, more preferably less than 200 DEG C.When heating-up temperature is below upper limit value, foaming body is not easy heat deterioration.Specifically, add Preferably 135~220 DEG C, more preferably 145~200 DEG C of hot temperature.
Expandable polymer more than the heat decomposition temperature of thermal decomposable foaming agent is foamed by being heated to.Foaminess is gathered Compound foams, and continues to expand on the hot plate of downside so that the hot plate of the foaming body contact upside of generation.Then, With the slow extruding foaming body of each hot plate up and down.
Then, preferably for example release the behaviour of the power of hot plate extruding foaming body by expanding the distance between a pair of of hot plate Make (extruding force release operation).By extruding force release operation, the density fluctuation of obtained foaming body tails off.
Then, between foaming body being held on a pair of of hot plate, in the state of by hot plate extruding foaming body, which is added More than heat to the heat decomposition temperature of thermal decomposable foaming agent, and then make its foaming.
After extruding force release operation, for the power by hot plate extruding foaming body, expansion ratio of foaming body etc. is considered to fit Preferably determine.
For the expansion ratio in foamed process entirety, determined according to purposes of acrylic resin foaming body etc. come suitable It is fixed.
The acrylic resin foaming body be suitable as the fuselage of such as aircraft, goods vehicle cold insulation room wall Material, the hull of small boat, the blade of wind-power electricity generation, daylighting heat-insulating material, the radiograph machine platform for making X-ray transparent, fortune Employ product (core of skiing, surfboard, racket handle etc.), for forming vehicle component (bucket seat, back desktop, small table plate (in arm table)) etc. component.
《Fiber-reinforced composite》
Hereinafter, the fiber-reinforced composite of the present invention is illustrated.
The fiber-reinforced composite of the present invention includes the acrylic resin foaming body and fibre reinforced plastics of the present invention.
As fibre reinforced plastics (FRP), it can include and reinforcing fiber bundles and integral are buried in the plastics as base material Change the plastics formed.As reinforcing fiber bundles, carbon fiber bundle, glass fiber bundle, boron fibre beam, aramid fiber beam can be included Deng.As plastics, epoxy resin, vinyl ester resin, unsaturated polyester resin, acrylic resin, polyamide can be included Resin, polycarbonate resin, acrylic resin, polyurethane resin etc..
The fiber-reinforced composite of the present invention can pass through the laminated fabric on the acrylic resin foaming body of the present invention Reinforced plastics is formed.
It is preferred that being heated under elevated pressure to the layered product after stacking, thus make acrylic resin foaming body and FRP pieces Bonding.
Pressure during bonding is preferably 0.1~1.0MPa, more preferably 0.2~0.8MPa.It should be noted that pressure can To be measured with attached pressure gauge of the attached pressure gauge of forcing press, autoclave etc., it is not particularly limited.
Temperature during bonding is preferably 60~180 DEG C, more preferably 90~160 DEG C.
In the fiber-reinforced composite of the present invention, the thickness of acrylic resin foaming body is preferably 1~60mm, more preferably For 3~40mm.
In the fiber-reinforced composite of the present invention, the thickness of fibre reinforced plastics is preferably 0.2~4mm, more preferably 0.2 ~2mm.
The ratio between the thickness of acrylic resin foaming body and the thickness of fibre reinforced plastics are with (acrylic resin foaming body Thickness)/(thickness of fibre reinforced plastics) represent, preferably 0.25~400, more preferably 0.5~200.
It should be noted that thickness can be measured by the method for the image viewing of electron microscope etc..
The fiber-reinforced composite of the present invention can possess fibre reinforced plastics in the single side of acrylic resin foaming body, Can also possess fibre reinforced plastics on the two sides of acrylic resin foaming body.
The fiber-reinforced composite of the present invention is in the fuselage of aircraft, the wall material of the cold insulation room of goods train, small boat Hull, wind-power electricity generation blade etc. in use.
More than, as described, acrylic resin foaming body of the invention has the heat resisting temperature in thermo-mechanical analysis Quantity for more than 170 DEG C, the bubble of major diameter 2mm above sizes is that every 10cm × 10cm areas are less than 2.0 such structures Into, thus, flexibility (adaptability) of operation, translucency, appearance and mechanical strength.
In addition, the manufacture method of the acrylic resin foaming body for the present invention, polymerizable monomer component includes opposite (methyl) acrylic acid for being 30~70 mass % in the gross mass of aforementioned polymeric monomer component, plasticizer are selected from by sulfonic acid At least one kind of compound in the group of ester, adipate ester and citrate composition.Therefore, it is possible to manufacture flexibility (adaptability) of operation, printing opacity The acrylic resin foaming body of property, appearance and mechanical strength.
In addition, acrylic resin foaming body of the fiber-reinforced composite of the present invention due to including the present invention, thoroughly Photosensitiveness, appearance and mechanical strength.
The acrylic resin foaming body of the present invention preferably makes polymerism polymerisation in solution as described below, foaming：It is poly- Conjunction property monomer component includes acrylic monomer；Pyrolytic foaming agent is selected from by urea, urea derivative, dinitroso five Methenamine, acid amides guanidine, trimethylene triamine, unifor, azodicarbonamide, thiocarbamide, ammonium chloride, dicyandiamide, It is at least one kind of in the group that dioxane, hexane, chloraldurate and citric acid form；Polymerization initiator is selected from by t-butyl peroxy Change hydrogen, cumyl hydroperoxide, diisopropylbenzene hydroperoxide, p-menthane hydroperoxide and 1,1,3,3- tetramethyl butyl peroxidating It is at least one kind of in the group of hydrogen composition；Plasticizer be selected from by adipate ester, trimellitate, polyester, phosphate, citrate, It is at least one kind of in the group that epoxidized vegetable oil, sebacate, azelate, maleate, benzoic ether and sulphonic acid ester form.
The acrylic resin foaming body of the present invention preferably makes following polymerism polymerisation in solution, foams to make：Polymerism Monomer component is the mixing for including methyl methacrylate, methacrylic acid, styrene, maleic anhydride and Methacrylamide Thing；Pyrolytic foaming agent is urea；Polymerization initiator is tert-butyl hydroperoxide；Plasticizer is selected from by alkyl sulfonic acid benzene It is at least one kind of in the group that ester, adipic acid isobutyl ester, acetyl tri-n-butyl citrate form.
Embodiment
Hereinafter, by embodiment and comparative example, more specifically the present invention will be described, but the present invention is not limited to following Embodiment.
[embodiment 1]
Relative to including 15 mass % of methyl methacrylate, 57 mass % of methacrylic acid, 16 mass % of styrene, horse Come 8 mass % of acid anhydrides, 100 mass parts of polymerizable monomer of 4 mass % of Methacrylamide, mix the uncle as polymerization initiator Butylhydroperoxide (Japan Oil Co's system " Perbutyl H-69 ") 0.5 mass parts, as metal ion (Cu2+) addition use The copper stearate (three Tianjin and chemicals Co. Ltd. system) 2.7 × 10 of material-3Mass parts, as chloride ion addition thing Cetyl trimethyl ammonium chloride (Japan Oil Co's system " Nissan Cation PB-40R ") 0.1 mass parts of matter, as poly- Close 0.2 mass parts of calcium formate, 2.0 mass parts of sodium sulphate as dehydrating agent, 5.0 mass of urea as foaming agent of inhibitor Part, 2.0 mass parts of Mesamoll as plasticizer, heating stirring is carried out at 35 DEG C, is filtered, removes the nothing of residue Machine salt, makes polymerism solution.
Obtained polymerism solution 1500g is put into the Teflon of the inside dimensions with 25mm × 200mm × 360mm The template of the rectangular-shape of (registration mark) system.
Then, polymerism solution is heated at 50 DEG C together with template 10 it is small when, then, it is small that 3 are heated at 80 DEG C When, thus obtain expandable polymer.
Thereafter, expandable polymer is put into recirculation furnace, is heated to urea (heat decomposition temperature：135 DEG C) decompose More than temperature (when specifically, heating 2 is small at 180 DEG C of in-furnace temperature), decompose foaming agent (urea), foaming, make The acrylic resin foaming body of 25mm × 200mm × 360mm.
[embodiment 2]
Methyl methacrylate is changed to 31 mass %, methacrylic acid is changed to 41 mass %, becomes plasticizer More adipic acid isobutyl ester, in addition, operates similarly to Example 1, makes acrylic resin foaming body.
[embodiment 3]
Methyl methacrylate is changed to 36 mass %, methacrylic acid is changed to 36 mass %, becomes plasticizer More acetyl tri-n-butyl citrate, in addition, operates similarly to Example 1, makes acrylic resin foaming body.
[embodiment 4]
Methyl methacrylate is changed to 36 mass %, methacrylic acid is changed to 36 mass %, becomes plasticizer More 1.0 mass parts, in addition, operate similarly to Example 1, make acrylic resin foaming body.
[embodiment 5]
Methyl methacrylate is changed to 41 mass %, methacrylic acid is changed to 31 mass %, in addition, with Embodiment 1 similarly operates, and makes acrylic resin foaming body.
[embodiment 6]
Methyl methacrylate is changed to 4 mass %, methacrylic acid is changed to 68 mass %, changes plasticizer For 1.0 mass parts, in addition, operate similarly to Example 1, make acrylic resin foaming body.
[embodiment 7]
Methyl methacrylate is changed to 36 mass %, methacrylic acid is changed to 36 mass %, becomes plasticizer More 0.1 mass parts, in addition, operate similarly to Example 1, make acrylic resin foaming body.
[embodiment 8]
Methyl methacrylate is changed to 36 mass %, methacrylic acid is changed to 36 mass %, becomes plasticizer More 20 mass parts, in addition, operate similarly to Example 1, make acrylic resin foaming body.
[comparative example 1]
Methyl methacrylate is changed to 47 mass %, methacrylic acid is changed to 25 mass %, in addition, with Embodiment 1 similarly operates, and makes acrylic resin foaming body.
[comparative example 2]
Methyl methacrylate is changed to 47 mass %, methacrylic acid is changed to 25 mass %, becomes plasticizer More dioctyl phthalate, in addition, operates similarly to Example 1, makes acrylic resin foaming body.
[comparative example 3]
Methyl methacrylate is changed to 36 mass %, methacrylic acid is changed to 36 mass %, becomes plasticizer More dioctyl phthalate, in addition, operates similarly to Example 1, makes acrylic resin foaming body.
[comparative example 4]
Be changed to 36 mass % of methyl methacrylate, 36 mass % of methacrylic acid, without using plasticizer, except this with Outside, operate similarly to Example 1, make acrylic resin foaming body.
The survey of Adaptability Evaluation, mean air bubble diameter is processed to the acrylic resin foaming body of each example as follows Fixed, the measure of apparent density, the measure of the quantity of stomata, the evaluation of translucency, the evaluation of mechanical strength, the evaluation of appearance.
It the obtained results are shown in table 1.
<Flexibility (adaptability) of operation is evaluated>
The heat resisting temperature of the acrylic resin foaming body of each example is measured by following step.
Foaming body is cut out as the rectangular-shape of 7mm (length) × 7mm (width) × 2mm (thickness), making test film.Use Thermal stress strain measurement device (SII NanoTechnology Inc. systems, trade name " EXSTRAR TMA/SS6100 "), It is using front endQuartzy manufacturing probe as pressure head.In compression test pattern, abutted on the thickness direction of test film The pressure head of load 100mN, test film is heated up with 5 DEG C/min of programming rate from 30 DEG C.The average thickness of determination test piece The temperature during average thickness shrinkage relative to the test film before experiment 10% is spent, using the temperature as heat resisting temperature.
It should be noted that the correction based on the setting of quartzy coefficient is carried out before parsing.In addition, being averaged for test film Thickness, makes 2 positions of test film the pressure head of load 100mN to abut test film to measure, obtains measurement result before the assay Average value.
According to heat resisting temperature, flexibility (adaptability) of operation is evaluated by following benchmark.
[metewand]
○：Heat resisting temperature is high, can obtain sufficient flexibility (adaptability) of operation.
×：Heat resisting temperature is low, cannot get sufficient flexibility (adaptability) of operation.
<The measure of mean air bubble diameter>
The acrylic resin foaming body of each example is cut off, with scanning electron microscope (Hitachi Ltd.'s system " S-3000N ") 18 times are amplified to, to adding up to 4 sections to shoot, the image of the section of shooting is printed onto A4 respectively On paper.
Then, 6 any line segments (length 60mm) are drawn to each A4 paper, according to the quantity of the bubble overlapping with the line segment, The mean chord of each line segment is calculated by following formula.Wherein, line segment is not only drawn by bubble in a manner of contacts as far as possible, In the case of contact, in the quantity of bubble.
The length of mean chord (t)=line segment/(multiplying power of quantity × photo of bubble)
Then, bubble diameter D is calculated by following formula.
D=t/0.616
Then, the arithmetic mean of instantaneous value for the bubble diameter D calculated by each line segment is obtained, using the arithmetic mean of instantaneous value as third The mean air bubble diameter of olefin(e) acid resin foam body.
<The measure of apparent density>
The apparent density of the acrylic resin foaming body of each example is utilized according to the JIS K 7222-1999 methods recorded Method measures.Specifically, for the 10cm cut off in a manner of not changing original foam structure3Test film above is surveyed Its fixed quality, apparent density is calculated by following formula.
Apparent density (g/cm3)=experiment tablet quality (g)/test film volume (cm3)
<The measure of the quantity of stomata>
The acrylic resin foaming body of 10cm × 10cm × 10cm is cut out from the acrylic resin foaming body of each example, is made For test film.To form the first section in any direction, second section orthogonal with foregoing first section and with foregoing first The mode in orthogonal the 3rd section in section and foregoing second section cuts off the test film.To 3 sections, scanning electron is used Microscope is observed, and obtains the sum of the bubble of major diameter 2mm above sizes, obtains the average value of every 10cm × 10cm areas.
<The evaluation of translucency>
Cut into slices to the acrylic resin foaming body of each example in thickness direction, obtain 10mm slabs, made For evaluation object.5 evaluation objects are obtained by 1 acrylic resin foaming body.
Obtained evaluation object is placed on light source, light difficulty penetrating region and the easy penetrating region of light is determined by visual observation, cuts Go out the section (dark portion section) in region comprising light difficulty penetrating region and region comprising the easy penetrating region of light (bright portion's section) Section, as test film.To 1 evaluation object, dark portion section and the section of bright portion are gathered at each 3.
According to JIS K 7361-1：1997 " test methods of the total light transmittance of plastics-transparent material ", the experiment to obtaining Piece measures total light transmittance by following determination conditions.The average value of the total light transmittance for the dark portion section obtained is cut into slices with bright portion Total light transmittance average value difference (printing opacity is poor), count evaluation object of the printing opacity difference less than 1.2, according to following metewands into Row evaluation.It should be noted that for embodiment 1, due to that can not determine that the easy penetrating region of light and light hardly possible pass through area by visual observation Domain, therefore undetermined total light transmittance, are evaluated as "○".
[determination condition]
Device：Mist degree transmitance meter (Heze-meter HM-150, Murakami K. K.'s dye technology research are made).
Assay method：Reference beam method (light source D65).
Test film：Length 50mm × width 50mm × thickness 10mm.
The adjusting condition of test film：It is adjusted when placement 20 is small in the environment of 23 ± 2 DEG C, humidity RH50 ± 5%.
Determination of the environment：20 ± 2 DEG C, humidity RH65 ± 5%.
[metewand]
○：There is no the inequality of light transmittance, be good quality (evaluation object of the printing opacity difference less than 1.2 is 4~5).
△：There is the inequality of light transmittance, but can utilize that (evaluation object of the printing opacity difference less than 1.2 is 2~3 according to purposes ).
×：The inequality of light transmittance is more (evaluation object of the printing opacity difference less than 1.2 is 0~1).
<The evaluation of mechanical strength>
To each acrylic resin foaming body, according to JIS A 9511：Described in 2006 " foamed plastic thermal insulation materials " Method, measures bending strength.
Specifically, using Tensilon universal testing machines UCT-10T (ORIENTEC CORPORATION systems), propylene is made The size of acid resin foaming body (test film) is 75mm × 300mm × 10mm, compression speed is 10mm/ minutes, is pressed from both sides in front end Have to be measured under conditions of pressurization wedge 10R, supporting table 10R, distance between the fulcrum 200mm, bending strength is calculated by following formula. The number of test film is set to 3, obtains its average value.
Bending strength (MPa)=3FL/2uh2
In formula, F represents bending maximum load (N), and L represents distance between the fulcrum (mm), and u represents the width (mm) of test film, h Represent the thickness (mm) of test film.
Bending strength so is obtained, the mechanical strength of acrylic resin foaming body is evaluated.
<The evaluation of the appearance of acrylic resin foaming body>
Each acrylic resin foaming body is visually observed, based on the following metewand, to acrylic resin foaming body Appearance evaluated.
[metewand]
◎：Stomata per 10cm × 10cm areas is less than 1.4
○：Per the stomata of 10cm × 10cm areas more than 1.4 and for less than 2.0
×：Per the stomata of 10cm × 10cm areas more than 2.0
[table 1]
It is according to table 1 as a result, it is possible to confirm to apply the acrylic resin foaming of the embodiment of the present invention 1~8 Heat resisting temperature of the body in thermo-mechanical analysis is more than 170 DEG C, and the quantity of stomata is that every 10cm × 10cm areas are less than 2.0, It is excellent in terms of translucency, appearance.In addition, the acrylic acid of the acrylic resin foaming body of embodiment 1~8 and comparative example 1~4 Resin foam body is compared, and bending strength is high.As shown in Figure 1, the acrylic resin foaming body of embodiment 1~8 meet Y >= 0.030X-0.351, intensity are especially high.
For comparative example 1~4, the quantity for being able to confirm that stomata is more than 2.0 per 10cm × 10cm areas, and processing adapts to Property, translucency, mechanical strength, poor appearance.The acrylic resin foaming body of comparative example 1~4 meets Y=0.027X-0.412's Relation, compared with embodiment 1~8, intensity is relatively low.
[embodiment 9]
The acrylic resin foaming body obtained in embodiment 1 is cut out as 500mm × 500mm × 20mm, is weighed on it Fibre reinforced plastics (MITSUBISHI RAYON CO., the LTD. trade names of folded 500mm × 500mm × 0.23mm " Pyrofil Prepreg TR3523-395GMP ", weight per unit area：200g/m2, thickness：0.23mm) each 2 layers of top layer, It is bonded them at pressure 1.5MPa, 135 DEG C of temperature, obtains fiber-reinforced composite.
[embodiment 10]
Using the acrylic resin foaming body obtained in embodiment 2, in addition, fibre is obtained similarly to Example 9 Dimension enhancing complex.
[embodiment 11]
Using the acrylic resin foaming body obtained in embodiment 3, in addition, fibre is obtained similarly to Example 9 Dimension enhancing complex.
[embodiment 12]
Using the acrylic resin foaming body obtained in embodiment 4, in addition, fibre is obtained similarly to Example 9 Dimension enhancing complex.
[embodiment 13]
Using the acrylic resin foaming body obtained in embodiment 5, in addition, fibre is obtained similarly to Example 9 Dimension enhancing complex.
[embodiment 14]
Using the acrylic resin foaming body obtained in embodiment 6, in addition, fibre is obtained similarly to Example 9 Dimension enhancing complex.
[embodiment 15]
Using the acrylic resin foaming body obtained in embodiment 7, in addition, fibre is obtained similarly to Example 9 Dimension enhancing complex.
[embodiment 16]
Using the acrylic resin foaming body obtained in embodiment 8, in addition, fibre is obtained similarly to Example 9 Dimension enhancing complex.
[comparative example 5]
Using the acrylic resin foaming body obtained in comparative example 1, in addition, fibre is obtained similarly to Example 6 Dimension enhancing complex.
[comparative example 6]
Using the acrylic resin foaming body obtained in comparative example 2, in addition, fibre is obtained similarly to Example 6 Dimension enhancing complex.
[comparative example 7]
Using the acrylic resin foaming body obtained in comparative example 3, in addition, fibre is obtained similarly to Example 6 Dimension enhancing complex.
[comparative example 8]
Using the acrylic resin foaming body obtained in comparative example 4, in addition, fibre is obtained similarly to Example 6 Dimension enhancing complex.
<The evaluation of the appearance of fiber-reinforced composite>
The appearance of observation gained fiber-reinforced composite by visual observation, based on the following metewand, answers fiber reinforcement Fit appearance is evaluated.
[metewand]
○：In fiber-reinforced composite, gauffer or the wire as caused by airtrapping etc. or mottled recess are sentenced for 2 Under.
△：In fiber-reinforced composite, gauffer or the wire as caused by airtrapping etc. or mottled recess produce 3~ At 4.
×：In fiber-reinforced composite, gauffer or the wire caused by airtrapping etc. or mottled recess produce 5 More than.
To obtained fiber-reinforced composite, the evaluation of appearance is carried out.
It the obtained results are shown in table 2.
[table 2]
It is according to table 2 as a result, it is possible to confirm to apply the acrylic resin foaming of the embodiment of the present invention 1~8 The appearance of the fiber-reinforced composite of body is excellent.
It is able to confirm that the poor appearance of the fiber-reinforced composite for the acrylic resin foaming body for having used comparative example 1~4.
Industrial applicability
In accordance with the invention it is possible to provide the acrylic compounds tree of flexibility (adaptability) of operation, translucency, appearance and mechanical strength Fat foaming body.
Description of reference numerals
1 acrylic resin foaming body
2 fibre reinforced plastics

Claims (11)

1. a kind of acrylic resin foaming body, wherein, the heat resisting temperature by following assay method A measure is more than 170 DEG C,
Quantity by the bubble of the major diameter 2mm above sizes of following assay method B measure is that every 10cm × 10cm areas are 2.0 It is a following,
Assay method A：
Using the acrylic resin foaming body of length 7mm × width 7mm × thickness 2mm as test film, thermo-mechanical analysis is used Device, is using front endQuartzy manufacturing probe as pressure head, under compression test pattern, in the thickness side of test film The pressure head of load 100mN is abutted upwards, is heated up from 30 DEG C with 5 DEG C/min of programming rate to test film, determination test piece Thickness relative to test film before experiment thickness contraction 10% when temperature,
Assay method B：
Using the acrylic resin foaming body that one side is more than 10cm as test film, in orthogonal three side of test film To section in, observed with scanning electron microscope, obtain the sum of the bubble of major diameter 2mm above sizes, and obtained Per the average value of 10cm × 10cm areas.
2. acrylic resin foaming body according to claim 1, it is to make containing the polymerization comprising acrylic monomer Property the propylene that forms of monomer component, thermal decomposable foaming agent, the polymerism polymerisation in solution of polymerization initiator and plasticizer, foaming Acid resin foaming body,
(the first that it is 30~70 mass % relative to the gross mass of the polymerizable monomer component that the polymerizable monomer component, which is included, Base) acrylic acid,
The plasticizer is at least one kind of compound in the group being made of sulphonic acid ester, adipate ester and citrate.
3. acrylic resin foaming body according to claim 1 or 2, its mean air bubble diameter is 0.05~0.30mm.
4. acrylic resin foaming body according to claim 2, wherein, the polymerism solution is relative to the polymerization Property 100 mass parts of monomer component contain 0.1~20 mass parts of the plasticizer.
5. acrylic resin foaming body according to claim 2, wherein, the polymerizable monomer component includes maleic acid Acid anhydride and (methyl) acrylamide.
6. a kind of fiber-reinforced composite, it includes acrylic resin foaming body according to any one of claims 1 to 5 and Fibre reinforced plastics.
7. a kind of manufacture method of acrylic resin foaming body, it is characterised in that make containing poly- comprising acrylic monomer Conjunction property monomer component, thermal decomposable foaming agent, polymerization initiator and plasticizer polymerism polymerisation in solution and producing foamed gathers Compound, makes the expandable polymer foam and acrylic resin foaming body is made,
The polymerizable monomer component includes (methyl) acrylic acid 30~70 relative to the gross mass of the polymerizable monomer component Quality %,
The plasticizer is at least one kind of compound in the group being made of sulphonic acid ester, adipate ester and citrate.
8. the manufacture method of acrylic resin foaming body according to claim 7, wherein, the polymerism solution includes Relative to the plasticizer that 100 mass parts of polymerizable monomer component are 0.1~20 mass parts.
9. the manufacture method of acrylic resin foaming body according to claim 7, wherein, the polymerizable monomer component Include maleic anhydride and (methyl) acrylamide.
10. a kind of sporting goods, it includes acrylic resin foaming body according to any one of claims 1 to 5.
11. a kind of vehicle component, it includes acrylic resin foaming body according to any one of claims 1 to 5.
CN201680051927.5A 2015-09-09 2016-06-29 Acrylic resin foaming body, its manufacture method and fiber-reinforced composite Pending CN107949600A (en)

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